Certain thiazolidine-thione alkhalides and process



United States Patent CERTAIN THIAZOLIDINE-THIONE ALKHALIDES AND PROCESS 1 Claims. 01. 260-3065) This invention relates to 2-thiazolidinethione alkhal ides, notably 2-thiazolidinethione methhalides, especially.

Z-thiazolidinethione methiodide, their preparation and application.

The compounds of this invention have the following structure wherein X is a halogen, preferably iodine, Y is sulfur wherein R is a lower alkyl group, and X is a halogen, preferably iodine.

A specifically preferred compound of the above' type i is 2-thiazolidinethione methiodide. This compound eX-. hibits utility in various applications where biological activity is advantageous as in phytocidal compositions, bactericides, defoliants, fungicides, and the like.

Other illustrative compounds in accordance with this invention comprise the methiodides of the following compounds:

CH3 Fliers. CH3 s NH 0 'NH I! H s s These compounds are less stable than 2-thiazolidinethione methiodide.

Compounds of this invention can generally be prepared by reacting carbon disulfide with ethylenimine or with ethanolamine and subsequently reacting the thusformed 2-thiazolidinethione with an alkyl halide, notably methyl iodide. The term alky as used herein is intended to include various alkyl groups, including methyl, ethyl, propyl, and the like, e.g., especially the lower alkyl radicals.

In order that those skilled in the art may more completely understand the present invention and the preferred method by which the same may be carried into eifect, the following specific examples are oifered:

2,953,573 Patented Sept. 20, 1960 EXAMPLE I Part A Preparation of 2 thiazolidine 2 thi0n'e.--To a crude canted and discarded. The resultant yellow methanol insoluble residue is boiled with 300 ml. of water for about 15 minutes and an aqueous layer decantedfroni the remaining yellow resin.

On cooling the decanted aqueous said yellow resin previously obtained are combined and boiled with water to obtain a second crop of crystals; the combined crystalline yield of thiazolidine-Z-thione being 28.5 gms. (0.25 mol), this material melting at Part B Preparation of Z-thiazolidinethione methiodide.-To 6 gms. of the product of Part A, recrystallized once from isopropanol, is added 7.2'gms. of methyl iodide.v This mixture is heated with 5-10-ml. of methanol. tion first becomes complete and then a light yellow material crystallizes. This solid is recrystallized three times by dissolving it in boiling methanol and filtering the solution into about 4 volumes of ether.

The resultant solid is triturated with ether, filtered and dried in a vacuum to yield a uniformly light yellow crystalline product weighing 8.9 gms. after crystallization. The resultant light yellow crystals melt at l10-114 C.

Chemical analysis of this product indicates preparation tion tests on glass slides are conducted via the test tube' dilution method adopted from the procedure recommended by the American Phytopathological Societys by counting 100spores.

committee on standardization of fungicidal tests. Inthis procedure the test chemical, in aqueous formulations at concentrations of 1000, 100, 10 and 1.0 p.p.m., is tested for its ability to inhibit germination of spores from 7 to lO-day-old cultures of Alternaria oleracea and Sclerotenia fructicala. These concentrations refer to initial concentrations' before diluting four volumes with one volume of spore stimulant and spore suspension. Germination records are taken after 20 hours of incubation at 22 C. The test compound is rated as to the concentration that inhibits germination of half of the spores, i.e., the so-called ED-SO value, in the test drops. Using this above procedure an ED-50 value of 10 to ppm. is obtained against each organism with Z-thiazolidinethione methiodide, thus indicating a marked degree of fungicidal activity.

EXAMPLE III The compound 2-thiazolidinethione methiodide is employed in a test as a tomato foliage treatment against infection by the Early Blight fungus Alternaria solani. This method employs tomato plants 5 to 7 inches high of the variety Bonny Best. Duplicate plants are sprayed with 100 ml. of the test formulation (2000 p.p.rn. test of methanol. After addition is" completed, the mixture is cooled and the methanol de-' 7 layer, crystals form which are removed by filtration. The residue and the 3 chemical-% acetone-0.01% Triton X-ISS-balance water) at 40 pounds air pressure while being rotated on a turntable in a spray chamber. After the spray deposit is dry, the treated plants and comparable untreated controls (sprayed with formulation less toxicant) are sprayed with a spore suspension containing'approximately 20,000 conidia of Alternaria solani per ml.

The plants are held in a saturated atmosphere for 24 hours at 70 F. to permit spore germination and infection before removal to the greenhouse. After 2 to 4 days, lesion counts are made on the three uppermost fully expanded leaves. The data are converted to percentage disease control based on the number of lesions obtained on the control plants.

Using the above procedure, a 63% control of the early blight fungus is observed thus indicating a marked degree of fungicidal effectiveness.

EXAMPLE IV To detect root absorption and translocation, corn and bean plants growing in 4 inch pots are treated by pouring 51 ml. of a 2000 p.p.m. test formulation (2000 p.p.m. 2 thiazolidinethione methiodide-5% acetone-0.01% Triton X-155-balance water) into pots (102 mg. per pot or approximately equivalent to 128 lbs. per acre). The thus-treated plants are held in the greenhouse for at least days before examination.

Using the above procedure, it is observed that 2-thiazolidinethione methiodide causes severe injury to the corn and kills the bean plants.

EXAMPLE V Bean plants, variety Tendergreen, just as the trifoliate leaves are beginning to unfold, are sprayed with 100 m1. of an aqueous test formulation of Z-thiazolidinethione methiodide at a concentration of 6400 ppm. (0.64%). Records are taken 14 days after treatment and phytotoxicity is rated on a scale from zero for no injury to 11 for plant kill. Using the above procedure, it is observed that the bean plants are killed.

EXAMPLE VI The 2-thiazolidinethione methiodide of Example I is mixed with distilled water, containing 5% acetone and 0.01% Triton X-155, at a concentration of 1000 ppm. Five ml. of the test formulation are put in each of 4 test tubes. Erewenia amylovora, Xanthomonas phaseoli, Staphylococcus aureus and Escherichia coli in the form of a bacterial suspension in a saline solution from potato-dextrose agar plates. The tubes are then incubated for 4 hours at 30 C. Transfers are than made to sterile broth with a, standard 4 mm. loop and the thus-inoculated broth incumbated for 48 hours at 37 C. when growth is rated as follows: A=no growth, B=slight, C=moderate and D=heavy growth.

Using the above procedure, with the Z-thiazolidinethione methiodide, ratings of B, B, B, and C, respectively are obtained against the above four organisms, thus indicating a high degree of bactericidal activity.

To each test tube is added one of the organisms:

While the compounds of this invention exhibit biological activity, the present invehtion does not necessarily contemplate that their use will be restricted to such application but that they will be useful in a variety of applications. In this connection, it will be appreciated that when employed in biological applications, as Well as other possible uses, they may well be utilized as formulations wherein they constitute but a minor amount of the total compositions. For example, they may be employed as essential ingredients in. various compositions including a major proportion of one or more diluents, extend ers, fillers, conditioners, solvents and the like, such as various clays, diatomaceous earth, talc, spent catalyst, alumina silica materials, and such liquids as water and various organic liquids such as acetone, kerosene, benzene, toluene, xylene and other petroleum distillate fractions or mixtures thereof. When liquid formulations are employed, or dry materials prepared which are to be usedv in liquid form, it is desirable in certain instances addi-.

tionally to employ a wetting, dispersing or other surfaceactive agent to facilitate use of the formulation, e.g., Triton X- (alkyl aryl polyether alcohol).

The term carrier as employed throughout the specification and claims is intended to refer broadly to the materials constituting a major proportion of a biologically active or other formulation and hence includes finelydivided materials, both liquids and solids, as aforementioned, conventionally used in such an application.

It is to be understood that although the invention has been described with specific reference to particular embodiments thereof, it is not to be so limited, since changesaction is. carried out in the presence of an organic solvent 6. The method according to claim 1 wherein the reaction is carried out in the presence of an organic solvent in which the product is insoluble.

7. The method of preparing Z-thiazolidinethione methiodide which comprises chemically combining 2- thiazolidinethione and methyl iodide.

References Cited in the file of this patent UNITED STATES PATENTS 2,284.577 Jones et a1 May 26, 1942 2,553,190 Harman May 15, 1951 2,756,135 Searle July 24, 1956 OTHER REFERENCES Shriner et a1.: Identification of Org. Compounds (Wiley, 3rd Ed.), pp. 179-80; 242-4 1948 

1. THE COMPOUNDS 2-THIAZOLIDINETHIONE ALKHALIDES. 